Preheat oven to 425°F/220°C/Gas 7.
Place the potatoes in the center of the oven and bake for approximately 50 minutes until cooked through. Remove the potatoes from the oven and transfer them to a baking rack to cool for 10 minutes or until they are cool enough to handle.
While the potatoes are cooling, place the tomato sauce, Italian seasoning, and garlic powder into a medium bowl. Season with salt and black pepper, to taste, and stir to combine. Set aside.
Once cool, cut the potatoes in half lengthwise and carefully scoop out the soft interior with a spoon, leaving a one-quarter inch margin around the skins. (Save the cooked potato filling for another recipe).
Place the potato skins cut side down on a baking rack set over a baking sheet. Brush the skins with olive oil and return to the hot oven for 10 minutes.
Remove the baking sheet from the oven and flip the skins over using tongs. Divide the seasoned tomato sauce evenly between the skins and spread into a thin layer with the back of a spoon.
Fill each skin with an equal amount of Mozzarella cheese, pepperoni, and fresh basil. Place back in the oven for another 10 minutes or until the cheese is melted.
Remove from the oven and cool for a few minutes before serving on top of extra-large basil leaves, if using. Enjoy!